Process for the ennoblement of textile materials and products therefrom



Patented Sept. 12, 1939 PATENT OFFICE rnocass FOR THE ENNOBLEMENT OF TEX- MAI-S TILE m FROM AND PRODUCTS THERE- Walther Kaase and Ernst Waltmann, Kreleld,

, amignors to- Heberlein Patent Cor- Germany notation, New York, N.-Y.',

New York a corporation of No Drawing. Application February 29, 1936, Se-

rial No. 66,498. Renewed October 6, 1938. Germany March 1, 1935 8 Claims.

This invention relates to increasing water-repellence in textile materials and particularly cellulose-containing materials; and to products obtained thereby.

In the ennobling of such textiles in the past in order to make them resistant to water there has been suggested a number of processes which are based mainly on the surface treatment 01' the said materials with esterifying agents such as fatty acid chlorides or fatty acid anhydrides. In the carrying out of these prior processes on a large scale considerable difliculties have been encountered due on the one hand to unfavorable reaction conditions whereby the appearance and feel of the goods is changed, and on the other hand because these processes require considerable time in operation as well as the expenditure of considerable money for materials.

The principal object of the present invention is to ennoble cellulose-containing materials such as cotton, jute, linen, hemp and rayon made of cellulose or derivatives of the same to render them resistant to water, by a simple process which may be carried out in a relatively short time and less expensively than heretofore; and to produce products having improved characteristics thereby.

The invention accordingly comprises the novel products as well as the novel processes and steps of processes according to which such products are manufactured, the specific embodiments of which are described hereinafter by way of example and in accordance with which we now prefer to practice the invention.

It has now been found that the ennobling of these textiles can be efiected within a very short period of time while at the same time giving the desired protection to the fibrous material if one subjects the textile materials to asymmetric fatty acid anhydrides, which may also be spoken of as asymmetric di-acyl oxides.

By the expression asymmetric fatty acid anhydrides there shall be understood those anhy-. drides which contain one acyl residue 0! at least carbon atoms while-the other acyl residue contains not more than 4 carbonatoms and preferably 2 carbon atoms. The principle involved in employing materials of this type 101' the treatment of these cellulose-containing materials is that these asymmetric anhydrides break up on heating so that from two mols of asymmetric duced on the fiber in the nascent state a fatty acid anhydrlde containing at least 10. carbon atoms and this fatty acid anhydride in the nascent state reacts with exceptional ease with the cellulose to cause esterification which is usually bon atoms on fatty acids containing' at least 10 carbon atoms.

In the place of the common fatty acids there may be employed with similar success fatty acids, the carbon chain of which is interrupted by atoms or atomic groups S, 0, 00.0, 0.00, NR,

NR.CO, CQNR, S02, NR.SO2, SO2.NR, in which B. may represent hydrogen or any desired hydro-' carbon residue. These compounds are covered herein by the expression-asymmetric fatty acid anhydrides-as defined above. I

As examples of useful products corresponding to the substances mentioned are the reaction ed with the substances just listed. The ketenes are selected to give an acyl residue of 4 carbon atoms or less. 1

- The new substances have great reactability with respect to such textile materials, especially the cellulose and cellulose derivatives here-. inabove mentioned, so that the action thereon takes place within a very short time without the need for special auxiliary reagents. It is only necessary to expose the materials impregnated with the mixed anhydrides to certaintemperatures with drying. First a preliminary drying at about 100 C. for evaporation of the solvent, if employed, occurs and subsequently a drying at an increased temperature of about 140-160" C.

for the splitting off and expelling of the anhydrides having the lower number of carbon atoms.

The impregnation oi the textile material with the products described may be efiected in any desired manner with or without the use of organic solvents, by emulsifying an aqueous solution of the anhydride and then treating the textile by immersion, spraying or the like. A catalyst may be employed for obtaining the desired Examples 1. A fabric of viscose warp and viscose crepe filling is passed through a 1% solution of asymmetric stearic acid-acetic acid anhydride in light benzene, suction filtered and thereupon exposed for 5 minutes to a temperature of 100 C. This is followed by a treatment at 150 C. for 5 minutes. The fabric thereupon has an excellent water-repellent property and its feel and the color have not been influenced in any manner whatsoever. This effect is also resistant to easy house laundering and is also not affected by treatments with organic solvents of the kind used by chemical cleaners. I

2. A fabric of a warp of acetate silk and a filling Of viscose crepe is sprayed with a 1% solution of adipic-acid-stearic alcohol ester-acetic acid anhydride in benzene and thereupon treated for 4 minutes at 100 C. This is followed by a treatment at 160 C. for 5 minutes. The fabric is thereupon water-repellent.

3. A fabric with a warp of acetate silk and a filling of viscose crepe is passed through a 1% solution of adipic-acid-stearic alcohol esteracetic acid-anhydride in benzene, thereupon ,treated for 1 minute at 100 C. and subsequently for 5 minutes at 150 C. The fabric is thereupon water-repelling.

As an example of the reaction which occurs upon treating textile material such as cellulosecontaining material with an asymmetric anhydride in accordance with our invention, whereby one component of the asymmetric anhydride is volatilized, we give the following reaction C "Has- C 0 O+HO.Cellulose-vC Il .C0.0.Cellulose cmoo +cmo00n Acetic acid (volatilizes) It will be noticed in this reaction acetic acid is liberated and volatilizes on heating under suitable conditions to cause a superficial esterification of the cellulose 'by the remainder of the asymmetric anhydride.

In the claims where the expression cellulosecontaining material" is employed it is intended to cover fibers, yarns, fabrics or other forms of cotton, jute, linen,.hemp and rayon including viscose, cuprammonium, or other precipitated cellulose or derivatives of cellulose such as acetyl cellulose.

While the invention has been described in detail according to the preferred manner of carrying out the process, it will be obvious ,to those skilled in the art after understanding the invention that changes and modifications may be made therein without departing from the spirit or scope of the invention, and it is intended in the appended claims to cover all such changes and modifications. 3

What is claimed as new and desired to be secured by Letters Patent is:

l. A process for the ennobling of textile materials which comprises applying to the textile material an asymmetric fatty acid anhydride containing a long acyl radical of at least 10 carbon atoms and a considerably shorter acyl radical capable of being split off upon heating, and heating tosplit off the shorter acyl radical and to cause a reaction of the textile material with the remainder of said anhydrlde.

2. A process for ennobling textile material which comprises applying to the textile material an asymmetric fatty acid anhydride having one acyl residue other acyl residue containing not more than 4 carbon atoms, to increase the water-repellence and to decrease the tendency to spotting of said material and heating to split off the acyl residue of not more than four carbon atoms to cause reaction of the textile material with the remainder of said fatty acid anhydride.

3. A process for ennobling cellulose-containing material which comprises applying to the textile material an asymmetric fatty acid anhydride having one acyl residue of at least 10 carbon atoms and another acyl residue containing not more than 4 carbon atoms, to increase the waterrepellence and to decrease tendency to spotting of said material and heating to about 100 C. or over to split off the acyl residue of not more than four carbon atoms to cause reaction of the textile material with the remainder of said fatty acid anhydride.

4. A process for ennobling cellulose-containing material which comprises treating cellulosecontaining material with an asymmetric fatty acid anhydride having two acyl residues, having one acyl residue of at least 10 carbon'atoms and the other acyl residue having not more than 4 carbon atoms, and heating the cellulose-containing material so treated to volatilize the acyl residue having the lower number of carbon atoms, to increase the water-repellence and to decrease tendency to spotting of said material.

5. A process according to claim 4 in which the anhydride is combined with the cellulose-containing material in the presence of a solvent and is thereafter heated first to remove the solvent and then to a higher temperature to break up the of at least 10 carbon atoms and arr-.-

anhydride and cause partial esterification of the cellulose by the acyl residue containing at least 10 carbon atoms.

adipic acid-stearic alcohol ester-acetic acid anhydride is substituted for, the stearic acid-acetic acid anhydride, followed by a heating to about 160 C. for about 5 minutes.

8. A cellulose-containing textile product being superficially combined with a fatty acid radical having at least ten carbon atoms, said material having a water-repellent property which is fast to washing but in appearance and feel being substantially the same as the untreated textile prodnot, said product being made according to the process of claim 1. I

WALTHER KAASE. ERNST WALTMANN.

CERTIFICATE OF. CORRECTION.

Patent no. 2,1'7'2,L 75. September 12, 19 9'.

WALTHER KAASE', ET AL. It is hereby certified that errorappears in the printed specification of the above numbered pateht re'quirihg correctionas follows: Page 2:, sec- 0nd column, line 20, claim 5, for "cellulose-containing" read textile; and

that the said Letters Patent should be read with this correction therein that the same may conform to the record of the case in the Patent Office.

Signed and sealed this 10th day of October, A; D. 19 9:,

, Hehry Van Aradale, (Seal) Actin commisaioner of Patents. 

